Method of making a piece of glass for measuring transmittance

ABSTRACT

In the measurement of internal transmittance of optical pieces, a standard is set for the piece for measuring the transmittance and a method of making the piece is provided. In the piece for measuring the transmittance of optical materials having two opposing polished surfaces, their surface roughness rms is set to 10 Å or less, thereby making it possible to accurately measure the internal transmittance in the short wavelength region of 300 nm or less where the intensity of the light source of spectrophotometer begins to decrease.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a piece (sample) used for accuratelymeasuring transmittance, e.g. internal transmittance (spectraltransmittance excluding reflection loss), of optical materials such asmulticomponent glass, synthetic silica glass, and crystal materials aswell as a method of making such a niece. In particular, it relates to apiece for measuring the transmittance of multicomponent glass used invisible-ultraviolet optical systems such as g-beam (436 nm) and i-beam(365 nm) lithography techniques and synthetic silica glass and crystalmaterials used in ultraviolet optical systems in the range of 300 nm orless such as KrF (248 nm) and ArF (193 nm) excimer laser lithographytechniques.

2. Related Background Art

An exposure apparatus called "stepper" has conventionally been used in aphotolithography technique in which a fine pattern of integratedcircuits is exposed to light and transferred to a wafer made of siliconor the like. The wavelength of the light source of the stepper has beenbecoming shorter as the integration of LSI increases.

SUMMARY OF THE INVENTION

It is necessary for the optical glass used in the illuminating system orprojection lens of such a stepper to have an internal transmittance of0.998 cm⁻¹ or 0.999 cm⁻¹ or more (i.e. internal absorption coefficientof 0.002 cm⁻¹ or 0.001 cm⁻¹ or less). As the LSI is further integrated,the light source of the stepper is shifting toward KrF and ArF excimerlasers. In the illuminating system or projection lens of such an excimerlaser stepper, generic optical glass cannot be used any more. Thematerial used for this purpose is restricted to such a material assilica glass or fluorite. It is also necessary for silica glass orfluorite used in the illuminating system or projection lens to have aninternal transmittance of 0.998 cm¹ or 0.999 cm⁻¹ or more. Accordingly,development has been in progress to increase the transmittance of theabovementioned optical materials in the ultraviolet region. As thewavelength becomes shorter, on the other hand, it has become technicallyvery difficult to accurately measure the internal transmittance of theoptical materials. Therefore, in the first place, in order to attain anoptical material with a high transmittance, it is necessary to provide atechnique by which the internal transmittance of optical glass,synthetic silica glass, crystal material, or the like with only a weakabsorption (with an internal absorption coefficient of about 0.001 cm⁻¹)can accurately be measured and evaluated.

As a method for measuring the internal transmittance, Japanese OpticalGlass Industrial Standard JOGIS-17-82 defines a method for measuring theinternal transmittance of optical glass. This method applies similarlyto other optical materials such as silica glass or crystal materialswhen the internal transmittance of such materials is to be measured.According to this standard, a pair of pieces for determining thetransmittance respectively having thicknesses of 3 mm and 10 mm areprepared, opposite surfaces of both pieces are polished in parallel toeach other, the internal transmittance is indicated as a value withreference to the 10 nm-thick glass, and the value is rounded off tothree decimal places. Therefore, the accuracy in measurement correspondsto an internal absorption coefficient of only 0.01 cm⁻¹ and cannot beapplied to short wavelength regions such as those of i-beam and excimerlaser where problems of errors in measuring the internal transmittancebecome critical.

In view of the foregoing, in order to measure an internal absorptioncoefficient of 0.001 cm⁻¹ as a significant difference in the method formeasuring the transmittance of optical materials, the inventors of thepresent invention have studied the following options:

1) Using a spectrophotometer with a high basic performance to determinethe spectral transmittance (i.e. transmittance including reflectionloss).

2) Compensating for a shift in transmittance due to a shift in anoptical path caused by a piece inserted within the measurement opticalpath.

3) Making a piece (sample) with a high accuracy, namely, with fewmeasurement errors.

In 1), it is preferable that the stray light in the measurement opticalpath or the measurement light noise of the measurement light detectingportion or the like should be in the range of ±0.0002 cm⁻¹ or less. Thislevel can be achieved when the kinds of commercial spectrophotometer areselected and their measuring condition is optimized.

The feature of 2) can be attained when the optical path of thespectrophotometer is adjusted and a calibration curve for the thicknessof the optical material is determined and corrected with reference toJapanese Patent Application No. 5-211217 titled "METHOD OF MEASURINGINTERNAL TRANSMITTANCE AND METHOD OF ADJUSTING SPECTROPHOTOMETER."

As for 3), there has conventionally been no standard for a sample usedfor measuring transmittance. Namely, items and levels have not beenquantified for specifying the sample. Accordingly, no method has beenindicated for making the piece for measuring transmittance whichembodies the standard thereof.

The present invention relates to 3) and aims at setting a standard for asample for measuring Transmittance in the measurement of the internaltransmittance of optical materials and providing a method of making sucha sample. The object of the present invention is to thereby measure aninternal absorption coefficient of 0.001 cm⁻¹ as a significantdifference and, in particular, to accurately measure the transmittancein the measurement of the internal transmittance in a short wavelengthregion of 300 nm or less where the intensity of the light source ofspectrophotometer begins to decrease.

For long years, in the method of measuring the transmittance of theoptical materials, the inventors have diligently studied errors in themeasurement caused by the standard of the sample for measuring thetransmittance and by the method of making the same.

In the first place, the inventors have studied the element of errors inmeasurement caused by the sample to find out that the parallelism,surface accuracy, and surface roughness of the polished surface of thesample can be problematic.

Therefore, as a standard for a sample for measuring the transmittance ofoptical materials, a standard is provided that the sample should have aparallelism of 30 seconds or less, a surface accuracy of the same orderas the parallelism or less, and a surface roughness rms of 10 Å or less.

In general, a part of the optical material to be evaluated is cut outinto a shape which can fit into a sample chamber of thespectrophotometer and its two surfaces opposing to each other in thethickness direction are optically polished with a commercial abrasiveagent to provide the aimed sample.

The parallelism used herein refers to an inclination (angle) withrespect to a reference surface which is one of the two opposingoptically-polished surfaces. The surface accuracy refers to an amount ofdeviation of the polished surface from a plane prototype. The surfaceroughness refers to the height of irregularities in eachoptically-polished surface.

Further, it has been found that the spectral transmittance of opticalmaterials decreases due to the structural defects resulting fromresidual impurities such as cutting and abrasive agents used for makingthe sample and residual stress generated upon processing of the sample.Accordingly, the present invention provides a method of making a samplefor measuring transmittance characterized in that the sample isprepolished to have a surface roughness rms of about 10 Å and thenpolished with an SiO₂ abrasive agent to have a surface roughness rms of10 Å or less or treated with an acid or alkali.

The piece according to the present invention, a transmittance of notless than 0.910 cm⁻¹ and not more than 0.921 cm⁻¹ with respect to alight beam having a wavelength of 248 nm. The piece according thepresent invention, a transmittance of not less than 0.895 cm⁻¹ and notmore than 0.908 cm⁻¹ with respect to a light beam having a wavelength of193 nm. The piece according to the present invention, wherein fluorineexists on said first flat surface and said piece has a transmittance ofnot less than 0.9210 cm⁻¹ and not more than 0.9211 cm⁻¹ with respect toa light beam having a wavelength of 248 nm. The piece according to thepresent invention, wherein fluorine exists on said first flat surfaceand said piece has a transmittance of not less than 0.905 cm⁻¹ and notmore than 0.908 cm⁻¹ with respect to a light beam having a wavelength of193 nm.

The present invention will become more fully understood from thedetailed description given hereinbelow and the accompanying drawingswhich are given by way of illustration only, and thus are not to beconsidered as limiting the present invention.

Further scope of applicability of the present invention will becomeapparent from the detailed description given hereinafter. However, itshould be understood that the detailed description and specificexamples, while indicating preferred embodiments of the invention, aregiven by wave of illustration only, since various changes andmodifications within the spirit and scope of the invention will becomeapparent to those skilled in the art from this detailed description.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph plotting the relationship between the surfaceroughness of a sample and its various transmittance values (248 nm).

FIG. 2 is a graph plotting the relationship between the surfaceroughness of a sample and its various transmittance values (193 nm).

FIG. 3 is a graph plotting the relationship between the amount ofresidual CeO₂ impurities and the spectral transmittance (248 nm).

FIG. 4 is a graph showing the behavior of the spectral transmittance(248 nm) with reference to methods of making the sample.

FIG. 5 is a graph showing the behavior of the spectral transmittance(193 nm) with reference to methods of making the sample.

FIG. 6 is a graph plotting the results of measurement of the 248 nmspectral transmittance of the synthetic silica glass in accordance withEXPERIMENT 1 of the present invention.

FIG. 7 is a graph plotting the results of measurement of the 193 nmspectral transmittance of the synthetic silica glass in accordance withEXPERIMENT 1 of the present invention.

FIG. 8 is a graph comparatively showing the spectral transmittancevalues of the synthetic silica glass in accordance with EXPERIMENT 2 ofthe present invention with reference to its qualities.

FIG. 9 is a graph plotting the results of measurement of the 248 nmspectral transmittance of fluorite CaF₂ in accordance with EXPERIMENT 3of the present invention.

FIG. 10 is a graph plotting the results of measurement of the 193 nmspectral transmittance of fluorite CaF₂ in accordance with EXPERIMENT 3of the present invention.

FIG. 11A shows a glass ingot.

FIG. 11B is a cross-sectional view of the glass ingot taken along theline X--X of FIG. 11A.

FIG. 12 shows a way of cutting a glass piece which has been cut out fromthe glass ingot of FIG. 11A.

FIG. 13 shows a glass piece which has been processed into a square form.

FIGS. 14, 15, 16, and 17 are drawings for explaining a polishing method.

FIG. 18 shows a unit for manufacturing a sample.

FIG. 19 shows a cross-sectional view of a sample holder.

FIG. 20A shows a sample which has been polished and etched.

FIG. 20B is a cross-sectional view of the sample taken along the line Zof FIG. 20A.

FIG. 21 shows a sample which has been made from an ingot of fluorite inthe same manner as noted above.

FIG. 22 is a view of a preform and a system for making the preform.

FIG. 23 shows the preform.

FIG. 24 shows the preform.

FIG. 25 shows a way of cutting a glass piece which has been cut out fromthe glass ingot of FIG. 24.

FIG. 26 shows a glass piece.

FIG. 27 shows a member of a holder.

FIG. 28 shows a cross sectional view of the member of FIG. 27.

FIG. 29 shows the holder and the pieces.

FIG. 30 shows a cross sectional view of the combined holder.

FIG. 31 shows a measuring system.

FIG. 32 shows a measuring system.

FIGS. 33-34 are cross sectional views of a piece.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

In the following, embodiments of the present invention will beexplained.

In order to make a piece of glass, an ingot 1 shown in FIG. 11A is used.FIG. 11B shows a cross-section of the ingot 1 taken along the line X--X.This cross section is circular.

A silica glass ingot with a high purity, which is an optical material,was synthesized by a process comprising the steps of preparing, as a rawmaterial, silicon tetrachloride with a high purity; using a burner madeof silica glass to mix and burn oxygen gas and hydrogen gas; dilutingthe raw-material gas with a carrier gas (which is usually oxygen gas)from the center portion so that the former gas gushes out; depositingthe gushed material on a target; and melting the deposited material. Inthis way, a silica glass ingot having a diameter of 180 mm and a lengthof 550 mm was obtained.

In the first place, a glass piece 1a is cut out from the ingot 1 along aplane perpendicular to the center axis of the ingot 1. Then, as shown inFIG. 12, a diamond saw 2 is used to cut the glass piece 1a in itsthickness direction to form a glass piece 1b such as the one shown inFIG. 13. The surfaces of the glass piece 1b are rough.

Thereafter, a manufacturing unit shown in FIG. 18 is used to process theglass piece. At first, as shown in FIG. 14, an abrasive agent 3aincluding cerium (Ce) is dispersed over glass sheet 3. A materialincluding CeO₂, Al₂ O₃, ZrO₂, diamond or the like is applicable as theabrasive agent Then, the glass sheet 3 is sprinkled with water 3b suchthat the abrasive agent 3a and water 3b are mixed together. As shown inFIG. 15, the glass piece 1b is moved on the glass sheet 3 in a circle soas to polish its upper and lower surfaces.

A surface roughness meter is used to examine the surface roughness ofthe glass piece 1b. When the surface roughness falls down to 100 Å orless, the glass piece 1b is placed within a container 5a in anultrasonic cleaner 5 to drop off Ce from the surface thereof. Thecontainer 5a has been filled with deionized water. The glass piece 1b iswashed within this container 5a for 5 minutes.

Thereafter, an abrasive agent 4a made of SiO₂ is used to further polishthe glass piece 1b. As shown in FIG. 16, the abrasive agent 4a isdispersed over a glass sheet 4. Then, the glass sheet 4 is sprinkledwith water 4b such that the abrasive agent 4a and water 4b are mixedtogether. As shown in FIG. 17, the glass piece 1b is moved on the glasssheet 4 in a circle so as to polish its upper and lower surfaces. Asurface roughness meter is used to examine the surface roughness of theglass piece 1b. When the surface roughness of the glass piece 1b fallsdown to 10 Å or less, the polishing step is over. The surfaces of theglass sheets 3, 4 are flat.

As noted above, the surface roughness meter is used to examine thesurface roughness of the glass piece 1b. When the surface roughnessfalls down to 10 Å or less, the glass piece 1b is placed within acontainer 5b in the ultrasonic cleaner 5 to drop off SiO₂ from thesurface thereof. The container 5b has been filled with deionized water.The glass piece 1b is washed within this container 5b for 5 minutes.

Thereafter, the glass piece 1b is taken out from the container 5b andplaced within a container 6 which has been filled with an aqueousfluoric acid (HF) solution. The glass piece 1b is immersed in an aqueousfluoric acid solution having a concentration of 5-20% by weight at15°-30° C. for 30 seconds to 3 minutes. Then, the glass piece is takenout from the container 6 and placed within a container 7 which has beenfilled with deionized water.

Thereafter, the glass 1b is taken out from the container 7 and placedwithin a container 8 which has been filled with nitric acid. The glasspiece 1b is immersed in an aqueous nitric acid solution having anormality of 0.01-0.05 at 15°-30° C. for 1-3 minutes.

Then, the glass piece 1b is taken out from the container 8 and placedwithin a container 9 which has been filled with aqueous ammonia. Theglass piece is immersed in an aqueous ammonia solution having anormality of 0.001-0.05 at 15°-30° C. for 1-3 minutes. Finally, theglass piece 1b is taken out from the container 9 and dried while beingsupported by its four corners alone. A special holder 10 is used forsupporting the glass piece 1b. FIG. 19 shows a cross-sectional view ofthe holder 10. This holder 10 comprises a lower member 10a and an uppermember 10b. When these members are combined together, the cross sectionof the holder 10 has an opening AP which is in an equilateral octagonshape. The opening AP is defined by eight sides. The four corners of theglass piece 1b abut to four of these eight sides. The opening AP isconstructed when a gutter formed on the lower member 10a and a gutterformed on the upper member 10b are combined together. Accordingly, whenthe glass piece 1b is placed within the gutter of the lower member 10aand then held by the inner surface of the gutter of the upper member10b, the glass piece 1b is supported within the opening AP. On the uppersurface of the lower member 10a, a hole 110a is formed to receive aprotrusion 10b of the upper member 10b so that the glass piece 1b isfixed within the holder 10.

FIG. 20A shows the dried glass sheet (piece)1b. FIG. 20B is across-sectional view of the glass piece 1b taken along the line Z ofFIG. 20A. The sample 1b has a pair of flat surfaces 11a, 11b opposing toeach other. The angle of these surfaces 11a, 11b with respect to eachother is 30 seconds or less. The roughness of each of the surfaces 11a,11b is 10 Å or less.

The shift in measurement light which influences the parallelism andtransmittance of the sample is expressed by the following equation:

    ΔX=θ1

wherein ΔX is the amount of displacement of the measurement light on adetector, θ is the parallelism of the sample, and 1 is the distancebetween the sample and the detector.

This equation indicates it necessary to define the parallelism of thesample in order to relatively compare transmittance values. Also, as thedirection of the sample with respect to the measurement light determinesthe direction of displacement of the measurement light on the detector,it is necessary for the direction of inclination of the sample to bealigned, preferably, at the time of measurement. However, the results ofour experiment have shown that errors in measurement can be neglectedwhen the parallelism is 30 seconds or less.

A fringe-scan type interferometer was used to measure the surfaceaccuracy.

The surface accuracy which provides a vertical difference in the sameorder as the above-defined parallelism (30") of the sample can beobtained from the following equations:

    surface accuracy=dλ

    d=tan(30")×L/λ/2

wherein λ is the wavelength of the measurement light which is usually546 nm, 2 is the number of the surfaces, L is the maximum length (cm) ofthe polished surface of the sample such as its diameter or diagonal linelength. Accordingly, the surface accuracy of 1.33Lλ or less isnecessary. It has been found that there are no problems concerning theaccuracy in measurement when the actually measured surface accuracy isset at a value not more than the surface accuracy obtained from theabove equations. From the above equations, d is determined as d=1.33L.The parallelism and the surface accuracy is explained in more detailusing FIGS. 33 and 34, respectively. The parallelism is defined as anangle θ between the lower surface 11b and the upper surface 11a. Thesurface accuracy is defined as a total length (A+B) as shown in FIG. 34.The length A is a maximum distance between parallel two virtual planeseach of which abuts a predetermined point on the diagonal line of uppersurface 11a. The length B is a maximum distance between parallel twovirtual planes each of which abuts a predetermined point on the diagonalline of lower surface 11b. The length (A+B) is less than 8 times λ 4368nm.

As to the surface roughness, in particular, the inventors have conductedexperiments for examining the sample standard by taking account of thefact that the spectral transmittance of optical materials is measuredlower than the theoretical transmittance calculated from theirrefractive index. An example of these experiments will be explainedbelow.

In the first place, the theoretical transmittance will be explained. Thespectral transmittance T in consideration of multiple reflection isdefined by the following equations (1) and (2): ##EQU1## wherein a isthe absorption coefficient, t is the thickness of the sample, and R isthe reflectivity when the measuring light is vertically incident on thesurface of the optical material. ##EQU2## wherein n_(g) is therefractive index of the sample and no is the refractive index of theair.

The theoretical transmittance T₀ is calculated as the spectraltransmittance in equation (1) when the decrease in the amount of lightresults from reflection loss alone, i.e. the internal absorptioncoefficient a is zero, or when the thickness of the sample isinfinitesimal.

In general, one of the reasons why the spectral transmittance iscalculated lower than the theoretical transmittance, i.e. there issurface loss in the amount of measured light, has been attributed to thescattering loss resulting from the surface roughness of the sample.

FIGS. 1 and 2 show relationships between the surface roughness of thesample and the theoretical transmittance excluding the scattering lossat measuring wavelengths of 248 nm and 193 nm, respectively.

The theoretical transmittance T(S) excluding the scattering loss iscalculated according to the following equation:

    T(S)={t-(S1.sup.r +S1.sup.t)}{t-(S2.sup.r +S2.sup.t)} 1+{R-(S2.sup.r +S2.sup.t)}.sup.2 !

wherein R is the reflectivity, t is the spectral transmittance 1-R afterpassing through the first surface, S1^(r) is the scattering loss of thereflected light at the first surface, S1^(t) is the scattering loss ofthe transmitted light at the first surface, S2^(r) is the scatteringloss of the reflected light at the second surface, and S2^(t) is thescattering loss of the transmitted light at the second surface.

The scattering loss values S1^(r), S1^(t), S2^(r), and S2^(t) arecalculated by the following equations:

    S1.sup.r =r(4πσ/λ).sup.2

    S1.sup.t =t{2π(n-1)σ/λ}.sup.2

    S2.sup.r =r(4πσ/λ).sup.2

    S2.sup.t =t{2π(n-1)σ/λ}.sup.2

wherein σ is the surface roughness rms of the sample (root mean square)expressed by Å, n is the refractive index of the sample, and λ is thewavelength of the measuring light.

Synthetic silica glass samples which had been made in the same mannerexcept for their surface roughness values to have a parallelism of 30seconds, a surface accuracy of 3λ, and a thickness t of 10±0.05 mm wereused as samples for measuring the spectral transmittance values withrespect to various surface roughness levels shown in the drawings.

The surface roughness can be measured by an optical interference typesurface roughness meter and determined by the following equation:##EQU3## wherein d(x,y) is the vertical difference at the position of(x,y) and n is the number of the whole data within the range ofmeasurement.

As can be seen from FIGS. 1 and 2, the theoretical transmittance valueexcluding the scattering loss shifts from the theoretical transmittanceat the measuring wavelength, i.e. 0.921194 cm⁻¹ at 248 nm and 0.908734cm⁻¹ at 193 nm, as the surface roughness of the sample increases.

These results indicate that, in order to secure the measuring accuracy,it is theoretically necessary for a standard for the sample formeasuring the transmittance to have a surface roughness of 10 Å or less.

In view of the foregoing, in the method of measuring the transmittanceof the optical materials, the present invention provides a standard forthe sample for measuring the transmittance that the sample has aparallelism of 30 seconds or less, a surface accuracy in the same orderas the parallelism or less, and a surface roughness rms of 10 Å or less,thereby making it possible to stably measure the internal absorptioncoefficient of 0.001 cm⁻¹ as a significant difference.

However, it is understood that the spectral transmittance is not onlyinfluenced by the surface roughness but can be measured lower than thetheoretical transmittance excluding the scattering loss by 0.001 cm⁻¹ ormore. This phenomenon is remarkable, in particular, at the shortwavelength of 193 nm.

Therefore, the inventors have further diligently studied the method ofmeasuring the transmittance of optical materials and investigated themethod of making the sample for measuring the transmittance. As notedabove, since the surface loss which causes the spectral transmittance todecrease cannot be explained by the scattering loss alone, variousmeasurements on the surface of the sample have been conducted.

The residual impurities on the surface of the sample could notquantitatively be analyzed by normal surface analysis methods such asESCA (electron spectroscopy for chemical analysis or X-ray photoelectronspectroscopy) and X-ray fluorescence analyzer since there are problemsconcerning their sensitivity. Accordingly, a total reflection X-rayfluorescence analyzer was used for analysis. The results are as follows:

a) A plenty of Ce impurities were detected on the surface of the samplewhose spectral transmittance had been detected particularly low.

b) The spectral transmittance at 193 nm was measured lower in some ofthe samples in which Ce impurities could not be detected by the totalX-ray fluorescence analysis method.

FIG. 3 shows a relationship between the amount of residual Ce impuritiesand the spectral transmittance at 248 nm. As shown by this drawing,surface loss is greater in the sample having a larger amount of residualCe impurities. This seems to be due to the fact that CeO₂, which is amain ingredient of the abrasive agent used when making the sample,remains in minute cracks on the surface of the sample. As the impuritiesremaining on the surface of the sample, there may be various ingredientscontained in the abrasive agent in addition to CeO₂, Al₂ O₃, and ZrO₂,which are main ingredients of the abrasive agent for optical materials,as well as diamond grinder particles and the like. Surface loss similarto that noted above may be caused when these ingredients remain on thesurface of the sample as a very small quantity of impurities.

Also, at a further shorter wavelength region, the results of b) seem tobe obtained as the influence of organic residue having an amount smallerthan the limit of detection or the impurities other than Ce or theinfluence of the structural defects resulting from the residual stressincreases for the reason not elucidated yet.

In view of these facts, it has become clear that, as a factorinfluencing the measurement of transmittance other than the surfacescattering of the sample, the influence of loss caused by the absorptionon the surface of the sample is great.

Therefore, in the method of measuring the transmittance of opticalmaterials, the inventors have studied the method of making a sample formeasuring transmittance by which an internal absorption coefficient of0.001 cm⁻¹ can accurately be measured as a significant difference. As aresult, it has been found out that the following points are effective:

(A) As optical polishing for making the sample, after prepolishing thesample with a commercial abrasive agent, polishing it with an SiO₂abrasive agent so as to attain a surface roughness rms of 10 Å or less

(B) After prepolishing the sample with a normal optical polishingtechnique, treating the surface of the sample with an acid or alkaliseveral hours before its transmittance is measured.

In (A), since CeO₂ itself, which is generally used as a commercialabrasive agent, tends to remain as impurities and causes thetransmittance to decrease, the abrasive agent should preferably includeingredients which are hard to remain or do not cause surface absorptioneven when they remain. In this respect, an abrasive agent mainlycomposed of fine SiO₂ particles, from which grinder particles andabrasive agents with a high purity can be obtained, is effective.However, when only the SiO₂ abrasive agent is used for polishing, thepolishing speed becomes slow and the working efficiency decreases. Whenonly the finish polishing is effected with the SiO₂ abrasive agent, onthe other hand, the residual impurities on the surface can effectivelybe removed while maintaining a desirable working efficiency.

Like (A), the residual impurities on the surface of the sample can beremoved in (B). In addition, it is expected that minute cracks may beremoved and residual stress may be alleviated to eliminate structuraldefects. Accordingly, (A) and (B) may be combined together to furtherimprove the accuracy in measurement.

From FIG. 3, the amount of residual Ce impurities where the internalabsorption coefficient becomes 0.001 cm⁻¹ is estimated as 4×10¹²atoms/cm². Accordingly, the amount of residual Ce impurities in thesample for measuring the transmittance should be 4×10¹² atoms/cm² orless.

When the amount of Ce impurities is zero, the difference between thetheoretical transmittance value and the spectral transmittance is about0.001 cm⁻¹. This difference seems to be mainly attributable to residualstress. Accordingly, the sample for measuring the transmittance shouldpreferably be free from residual stress.

As means for the acid or alkali treatment, an acid treatment solutionsuch as HF, HNO₃, or mixed HF+H₂ SO₄ solution, an alkali treatmentsolution such as aqueous NH₄ OH solution, or a technique for exposingthe sample to an acid or alkali atmosphere may be used.

Various conditions for the acid or alkali surface treatment of thesample, e.g. the concentration of the aqueous solution, temperature, andtime of treatment, can voluntarily be set in view of the chemicaldurability of the sample. It is desirable, however, for the surfacetreatment here to attain an erosion depth in the order of about 0.01-0.1μm and a surface roughness rms of not more than 10 Å.

The surface treatment of (B) is effected several hours before themeasurement since it has experimentally been proved that the surfaceloss increases when the sample is left for a long time. Though notelucidated yet, this seems to be attributable to a factor which issimilar to a chemical deterioration on the surface of the sample called"burning." Also, attention should sufficiently be paid to the cleaningand drying of the sample after the acid or alkali treatment so as not tocause any chemical deterioration.

Among the acid treatment means, the HF treatment is particularlyeffective in removing the residual impurities since its aqueous solutionwith a high purity can easily be obtained. In this case, a very smallquantity of F remains on the surface of the sample after the treatment.This remaining F can be detected as Si--F or Si--O--F by ESCA or SIMS(secondary ion mass spectrometer). It is desirable for the sample formeasuring transmittance to have a very small quantity of F to bedetected while containing no other impurities. Of course, the crystal oroptical glass containing F as its composition should be handled in adifferent way.

The effect obtained by the method of making the sample in accordancewith the present invention will be examined while synthetic silica glassis used as an example.

Usually, when a minute absorption of transmittance is to be evaluated,the dependence of the transmittance upon the thickness of the sample ismeasured and the absorption coefficient, a cm⁻¹, is calculated.Accordingly, the spectral transmittance with respect to the thickness ofthe sample was measured at measuring wavelengths of 248 nm and 193 nm.Its results are shown in FIGS. 4 and 5.

The sample was made to have, as a standard, a parallelism of 30 secondsor less, a surface accuracy in the same order as the parallelism orless, and a surface roughness rms of 10 Å or less.

In the first place, the optical polishing surface was subjected tofinish polishing with an SiO₂ abrasive agent and then its spectraltransmittance was measured. Further, the same sample was immersed in a10% aqueous HF solution at about 20° C. for about 1 minute to effect asurface treatment and then its spectral transmittance was similarlymeasured. AFM (atomic force microscope) inspection confirmed that the HFtreatment of the sample had yielded an erosion depth of about 0.08 μmand had not deteriorated but slightly improved the surface roughness.

As shown in FIG. 4, at the measuring wavelength of 248 nm, the spectraltransmittance of the sample finished with the SiO₂ abrasive agentsubstantially coincides with the theoretical transmittance. Also,similar results were obtained when the sample was treated with HF.

At the measuring wavelength of 193 nm shown in FIG. 5, while the finishpolishing with the SiO₂ abrasive agent effectively reduced the surfaceloss of the conventional polishing, the resulting spectral transmittancefailed to coincide with the theoretical transmittance. When the samplewas treated with HF, its result of measurement coincided with thetheoretical transmittance.

Therefore, as a method of making a sample for measuring thetransmittance of optical materials, it is effective to conduct a finishpolishing step with an SiO₂ abrasive agent as well as an acid or alkalitreatment step. In particular, at 300 nm or less, both steps can becombined together to further increase the accuracy in measurement.

EXPERIMENT 1

The above-mentioned silica glass piece 1b was cut out from the ingot 1as a sample for evaluating the accuracy in measurement of transmittanceobtained by the present invention and for comparing the measured valuewith the theoretical transmittance.

The used method of measuring the internal transmittance of the silicaglass having a high purity comprises the steps of preparing 5 pieceseach of 5 kinds of samples with different thickness values, measuringtheir spectral transmittance values at 248 nm and 193 nm, andcalculating the internal transmittance from the measured values (cf.Japanese Patent Application No. 5-211217). The form of the sample andconditions for making the same are as follows:

Form: Φ60×t1, 5, 10, 20, 28±0.01 mm

Number: 5 pieces for each thickness value

Surface Accuracy: 3λ(λ=546 nm)

Parallelism: 10 seconds

Surface roughness: rms 2 Å

Finish polishing: fine SiO₂ particle

Acid treatment: 10% aqueous HF solution (20° C., 1 minute)

Each of FIGS. 6 and 7, in which the results of measurement are plotted,has x-axis for thickness and y-axis for the transmittance includingreflection loss. The average of the measured values for each thicknesshas been calculated and plotted. Also, the average at each thickness isapproximated by a line.

The repeated reproducibility levels of the measured values, in which thelevels of accuracy in the spectrophotometer and sample have been takeninto account, are within the ranges of ±0.0001 cm⁻¹ and ±0.0005 cm⁻¹ atthe measuring wavelengths of 248 nm and 193 nm, respectively.

1) At the measuring wavelength of 248 nm, the approximate expression isobtained from FIG. 6 as follows:

    Y=0.9231197-3.08×10.sup.-6 X

The transmittance value including the reflection loss at 10 mm-thicknesswas obtained by this equation and the 10 mm-internal transmittance valueat 248 nm was calculated in accordance with the following equations:

    10 mm-transmittance including reflection loss 0.921166 cm.sup.-1

wherein: ##EQU4## 2) At the measuring wavelength of 193 nm, theapproximate expression is obtained from FIG. 7 as follows:

    Y=0.908751-7.13×10.sup.-6 X

As in the case with 1), the 10 mm-internal transmittance value at 193 nmwas calculated as follows:

    10 mm-transmittance including reflection loss 0.908680 cm.sup.-1

wherein: ##EQU5## These results show that, when the standard for thesample and method of making the same in accordance with the presentinvention are used, repeated reproducibility of the transmittanceincluding reflection loss is obtained at 248 nm and 193 nm withdifferences between their transmittance values and the theoreticaltransmittance of 2.8×10⁻⁵ cm⁻¹ and 5.4×10⁻⁵ cm⁻¹, respectively, whichyield an accuracy in measurement which is sufficient for studying aninternal absorption coefficient of 0.001 cm⁻¹.

Also, it is understood that this sample has an internal transmittance of0.999 cm⁻¹ or more. Further, when its internal absorption loss is takeninto account, it is considered that there is substantially no internalabsorption in practice.

When the surface of the sample was analyzed with the total reflectionX-ray fluorescence method, Ce impurities were not more than the limit ofdetection. Further, a very small amount of F was detected upon itsmeasurement.

Since the silica glass evaluated this time has a high quality, itsinternal absorption is very small. However, the absorption in the orderof 0.001-0.005 cm⁻¹, which is caused by reductants of SiO₂, Naimpurities, or the like, may sometimes be observed in those with a lowquality at about 200 nm to the shorter wavelength region. While thequality has conventionally been evaluated with the internal absorptionin such an order, smaller differences in the quality can be detected inaccordance with the present invention.

EXPERIMENT 2

Silica glass samples with different qualities were used to obtaintransmission spectra including reflection loss in the wavelength regionof 185-260 nm. A spectrophotometer, whose optical axis had been adjustedsuch that the deviation of the spectral transmittance from thetheoretical transmittance accompanying the increase in the thickness ofthe sample was within the range of ±0.0001 cm⁻¹ or less when thespectral transmittance at 365 nm was measured, was used for themeasurement (cf. Japanese Patent Application No. 5-211217). The form ofthe sample and conditions for making the same are as follows:

Type: A (high purity), B (general), C (general)

Form: Φ60×10±0.01 mm

Number: 1 piece each

Surface Accuracy: 3λ(λ=546 nm)

Parallelism: 20 seconds

Surface roughness: rms 8 Å

Finish polishing: none

Acid treatment: 10% aqueous HF solution (20° C., 1 minute)

The results of measurement is shown in FIG. 8 in which the wavelengthand the transmittance including reflection loss are respectivelyindicated at x-axis and y-axis. As shown in this drawing, the resultshave proved that sample A containing several ppb of metal impuritiessubstantially coincides with the theoretical transmittance at themeasuring wavelengths of 248 nm and 193 nm within an error level of 0.1%or less, while samples B and C containing several ten to several hundredmetal impurities do not coincide with the theoretical transmittance,thereby indicating that there is internal absorption in the silica glassof the sample.

Also, as the transmittance continuously changes with respect to themeasuring wavelength, it is understood that the surface of the samplethus manufactured is stable regardless of the wavelength andsufficiently satisfies the measuring accuracy at the measuringwavelength region of 250 nm or less.

In view of the foregoing, it can be judged that, while silica samples Band C satisfy the standard of 10 mm-internal transmittance of 0.999 cm⁻¹or more as a lens material for KrF excimer laser steppers, they cannotsatisfy the standard for ArF excimer lasers. Also, designed performanceof the stepper is expected to deteriorate when such materials as B and Care used.

EXPERIMENT 3

FIG. 21 shows a sample 1b which has been made from an ingot of fluorite.This sample is made in the same process and has the same structure asthe silica glass sample except for the materials used.

Bridgman method (also known as Stockberger method or crucible-descendingmethod) was used, while minutely controlling the temperature condition,descending speed, or the like, to cultivate a single crystal of fluorite1b having a diameter of 250 nm and a height of 300 mm.

Inductively coupled plasma spectrometry quantitatively analyzed thatthus obtained silica glass ingot and fluorite single crystal contained1b ppb or less of each metal impurities (Ti, Cr, Fe, Ni, Cu. Zn, Co, andMn). Namely, these silica glass and fluorite have a high purity.

The above-mentioned single crystal of fluorite was cut out as a sampleand, as in the case with EXPERIMENT 1, its spectral transmittance wasmeasured and evaluated at 248 nm and 193 nm.

Form: Φ60×t1, 5, 10, 20, 28+0.01 mm

Number: 5 pieces for each thickness value

Surface Accuracy: 3λ(λ=546 nm)

Parallelism: 10 seconds

Surface roughness: rms 2 Å

Finish polishing: fine SiO₂ particle

Acid treatment: 0.02N aqueous nitric acid solution (20° C., 1 minute)

Each of FIGS. 9 and 10, in which the results of measurement are plotted,has x-axis for thickness and y-axis for the transmittance including thereflection loss. The average of the measured values for each thicknesshas been calculated and plotted. Also, the average at each thickness isapproximated by a line.

The repeated reproducibility levels of the measured values, in which thelevels of accuracy in the spectrophotometer and sample have been takeninto account, are in the same order as those of EXPERIMENT 1.

1) At the measuring wavelength of 248 nm, the approximate expression isobtained from FIG. 9 as follows:

    Y=0.930216-4.36×10.sup.-6 X

The transmittance value including the reflection loss at 10 mm-thicknesswas obtained by this equation and the 10 mm-internal transmittance valueat 248 min was calculated in accordance with the following equations:

    10 mm-transmittance including reflection loss 0.930172 cm.sup.-1

wherein: ##EQU6## 2) At the measuring wavelength of 193 nm, theapproximate expression is obtained from FIG. 10 as follows:

    Y=0.922458-1.075×10.sup.- X

As in the case with 1), the 10 mm-internal transmittance value at 193 nmwas calculated as follows:

    10 mm-transmittance including reflection loss 0.922351 cm.sup.-1

wherein: ##EQU7##

From these results, it has been judged that the internal transmittanceis 0.999 cm or more at both 248 nm and 193 nm. When the internalscattering loss is taken into account, it can be judged that there issubstantially no internal absorption in practice. While the CaF₂ sampleevaluated here has such a high purity that only minute internalabsorption exists, several kinds of absorption bands may sometimes beobserved at visible to ultraviolet region in those with a poor quality.The sample in accordance with the present invention can be used formeasuring the transmittance to detect such a minute difference inquality.

When the standard for the sample and method of making the same inaccordance with the present invention are used, it has become possibleto accurately measure the internal transmittance of optical materialswith an error level of ±0.001 cm⁻¹ or less. The present invention iseffective, in particular, in the measurement of transmittance at a shortwavelength region of the ultraviolet region and at the vacuumultraviolet region.

Also, the present invention can be used for polishing optical componentsin which minute absorption at the short wavelength region isproblematic.

Next, a piece of a preform for an optical component according to asecond embodiment will be explained below. Regarding the following pieceand the method for fabricating the same, not described is as same as thepiece and the method described above.

The method for making the preform is explained by using FIGS. 22 and 23.The preform is fabricated by using a burner 20. The burner 20 isarranged closer to a SiC substrate 21. SiCl₄ gas, O₂ gas and Ha gas areintroduced into the burner 20, and these gases react with each other toform glass particles. The fluid of the glass particles, which isso-called soot, is transmitted to the substrate 21, and the glassparticles are deposited on the substrate 21 and melted at the time ofcolliding the glass particles with the substrate 21. The substrate 21 isrotated while the deposition is performed.

After the deposition, the preform 1 is cooled down to a roomtemperature. FIG. 23 shows the preform 1 under such a state.

The substrate 21 is detached from the preform 1 as shown in FIG. 24. Apiece according to the present embodiment is cut out from thispreform 1. A method of making the piece for measuring a transparency ofthe preform 1 is explained below.

First, the piece 1a is cut out from the preform 1 along dotted lines inFIG. 24, by using a diamond saw. Each of the dotted lines isperpendicular to the axis of the preform 1.

Second, a sub piece 1c near its periphery is cut from a main piece id ofthe piece 1a by using a diamond saw 2 as shown in FIG. 25.

Third, the surfaces of the piece 1d is treated as same as the surfacesof the piece 1b, except its drying step. That is, the piece 1d is takenout from the container 9 shown in FIG. 18 and dried while beingsupported by its corners alone. A special holder having a plurality ofmembers 210 is used for supporting the piece 1d. FIG. 26 shows the pieceafter this treatment.

This piece 1d has a front surface 21a and a back surface 21b. The anglebetween the surfaces 21a and 21b is less than 30 seconds, and thesurfaces 21a and 21b are substantially flat. The piece id has sidesurfaces 21c and 21d connecting the front surface 21a to the backsurface 21b. One 21c of the side surfaces is curved round, and the other21d is flat. The side surface 21c is almost cylindric and the angle 22at the circumference of the side surface 21c is larger than 270°.

FIG. 27 shows a perspective view of a member 210 of the holder, and FIG.28 is a cross-sectional view of the member 210 taken along the line Z--Zof FIG. 27.

The member 210 has a cylindrical outer surface 210c, and an outer threadpart 210b continued to the outer surface 210c via a lower lip 210m. Thediameter of the cylindrical outer surface 210c is greater than that ofthe thread part 210b. The member 210 has an inner thread portion 210aopposing to the outer surface 210c, and an inner cylindrical surface210e connected to the inner thread portion 210a via an inner lip 210d.An inner conical surface 210f is continued to the inner cylindricalsurface 210f, and a circular bottom surface 210g crosses the conicalsurface 210f at an obtuse angle. The upper inner surfaces forms an uppercavity of the member 210. The member 210 has a lower cavity which isarranged under the upper cavity. The lower cavity is formed by a lowercylindrical inner surface 210h opposing to the outer thread part 210b, alower conical surface 210i continued to the lower cylindrical innersurface 210h and a circular ceiling 210j which crosses the conicalsurface 210i at obtuse angle.

The holder consisting of a plurality of members 210 are shown in FIGS.29 and 30. Three members 210 and two pieces are sandwiched by themembers 210 are shown in FIGS. 29 and 30, and terms of "upper", "middle"and "lower" are used based on the drawings. The members 210 are combinedby fastening each of the outer thread surfaces 210b to each of the innerthread surfaces 210a. When these members 210 are combined together, thecross section of the holder has an opening AP which is almost in anoctagon shape. Nevertheless the thickness of the upper piece 1d isthicker than that of the lower piece 1d, the holder can hold both of thepieces 1d as shown in FIGS. 29 and 30. The piece 1d is supported by theconical surfaces 210f and 210i alone, thereby the member 210 is driedwhile the surfaces 21a, 21b, 21c and 21d are not in contact with theholder.

The piece 1d is evaluated by using a system shown in FIG. 30. Thissystem has an excimer laser light source 305 such as a KrF excimerlaser, a photo-mask 304 arranged in a pass way of the light, and aninfrared camera 300a for picking up an infrared image of the piece id.The laser light source 305 is mounted on a table 307 via a spacer 306.The photo-mask 304 is supported by a holder 304a, the piece 1d issupported by the a holder 301b and the camera 300a is supported by aholder 300b. All of the devices 304, 304a, 301b, 300a and 300b arearranged in a box such as a desiccator 303. The box 303 is filled withnitrogen gas. The gas is introduced into the desiccator 303 via a cock302.

After the piece 1d is fixed to the holder 301d, the evaluation isperformed. The excimer laser light source 305 emits a laser light beam,and the light passes through the photo-mask 304 and is emitted onto thepiece 1d. The infrared image of the piece 1d is detected by the IRcamera 300a. The data of the infrared image detected by the IR camera300a is corresponding to the temperature distribution in the piece 1d,and the temperature distribution is detected by a thermograph (ThermoTraser, NEC San-ei, type 6T62) using the IR camera 300a. The temperaturedistribution image is displayed on the display 300. Since the piece 1dhas a circular shape, the temperature distribution in the piece 1dbecomes uniform.

When the laser light is emitted onto the piece 1d, photoluminescenceoccurred in the piece 1d. The luminescence is emitted through the flatside surface 21d. An optical fiber 301a is optically coupled to the flatside surface 21d, and the luminescence is introduced into aspectrophotometer 301 (Ohtsuka Electronics, type IMUC7000) via the fiber301a.

The piece 1d is also evaluated by the Raman spectroscopic analysis. Asystem for this evaluation is shown in FIG. 32. This system has a darkbox 401, Ar laser light source 400 for emitting laser light 400a, beingarranged in the dark box 401, and a Raman spectrophotometer 402 fordetecting light 400b scattered in the piece 1d. The laser light beam400a is introduced into the piece 1d through the side flat surface 21d,and the Raman scattering is occurred in the piece 1d and the scatteredlight 400b is emitted through the upper surface 21a. Consequently, sincethe piece 1d has the above-described shape, it can be evaluated by manysystems. The piece 1d may be applicable to measuring a transmittance ofa glass as a standard sample.

From the invention thus described, it will be obvious that the inventionmay be varied in many ways. Such variations are not to be regarded as adeparture from the spirit and scope of the invention, and all suchmodifications as would be obvious to one skilled in the art are intendedto be included within the scope of the following claims.

What is claimed is:
 1. A method of making a piece of glass for measuringtransmittance, said method comprising the steps of:(a) polishing a firstsurface of a piece of silica glass with an abrasive agent including Ceuntil said first surface has a roughness of 100 angstroms or less: and(b) polishing said first surface of the piece with an abrasive agentmade of SiO₂ until said first surface has a roughness of 10 angstroms orless and the amount of Ce on said first surface is 4×10¹² atoms/cm² orless, after step (a).
 2. A method according to claim 1, wherein saidabrasive agents in steps (a) and (b) are mixed with water whenpolishing, and the method further comprising the step of processing thepiece with an alkaline solution.
 3. A method according to claim 1,wherein said piece is immersed in an aqueous fluoric acid solution afterstep (b).
 4. A method according to claim 1, wherein said piece isimmersed in an aqueous fluoric acid solution having a concentration of5-20% by weight after step (b).
 5. A method according to claim 1,further comprising, after step (b), the step of:immersing said piece inan aqueous nitric acid solution.
 6. A method according to claim 1,further comprising, after step (b), the step of:immersing said piece inan aqueous ammonia solution.
 7. A method according to claim 1, furthercomprising, after step (b), the step of:immersing said piece in anaqueous nitric acid solution having a normality of 0.01-0.05.
 8. Amethod according to claim 1, further comprising, after step (b), thestep of:(c) immersing said piece in an aqueous fluoric acid solutionhaving a concentration of 5-20% by weight at a temperature of 15°-30° C.for 30 seconds to 1 minute.
 9. A method according to claim 1, furthercomprising, after step (b), the step of:(d) immersing said piece in anaqueous nitric acid solution having a normality of 0.01-0.05 at atemperature of 15°-30° C. for 1-3 minutes.
 10. A method according toclaim 1, further comprising, after step (b), the step of:(e) immersingsaid piece in an aqueous ammonia solution having a normality of0.01-0.05 at a temperature of 15°-30° C. for 1-3 minutes.
 11. A methodaccording to claim 1, wherein said piece is rectangular and saidrectangular piece is dried after step (b), while said rectangular pieceis supported in a holder which has an inner surface that can contact toonly the four corners of said rectangular piece.
 12. A method accordingto claim 10, wherein said piece is in a rectangular shape having fourcorners and said method further comprising, after step (e), the step ofsupporting said piece by said four corners alone.
 13. A method accordingto claim 1, further comprising the step of measuring transmittance ofsaid piece.
 14. A method of making a piece of glass for measuringtransmittance, said method comprising the steps of:(a) polishing a firstsurface of a piece of silica glass with an abrasive agent including Ceuntil said first surface has a roughness of 100 angstroms or less; and(b) polishing said first surface of the piece with an abrasive agentmade of SiO₂ until said first surface has a roughness of 10 angstroms orless and an angle between said first surface and its opposite surface is30 seconds or less, after step (a).